Beidellite clay and process for preparing the clay

ABSTRACT

This invention relates to a novel beidellite layered clay, a process for preparing the clay and a process using the clay. The clay is characterized in that it is substantially free of sodium cations, is composed of crystals whose average crystallites size is about 50-150 Angstroms, has a surface area of at least 80 m 2  /g and has its 060 X-ray diffraction peak at a d-spacing of 1.50 Angstroms. The clay is prepared from a reaction mixture containing reactive sources of aluminum and silicon, a templating agent and water. Examples of templating agents are quaternary ammonium compounds such as tetramethylammonium hydroxide. Reactive source of aluminum and silicon include boehmite alumina and colloidal silica. The mixture is reacted at a pH of about 8.5 to about 14, a temperature of about 150° to about 210° C. for a time of about 1 to about 20 days. The clay composition may be used as is or after pillaring to catalyze hydrocarbon conversion processes such as alkylation.

FIELD OF THE INVENTION

This invention relates to a novel beidellite layered clay (one of thesmectite clays) composition, a process for preparing the clay, and aprocess using the clay. The clay is characterized in that it hascrystals whose average crystallite size is about 50-150 Angstroms, has asurface area of at least 80 m² /g, has its 060 X-ray diffraction peak ata d-spacing of 1.50 Angstroms and is substantially free of sodiumcations. The clay is prepared from a reaction mixture containingreactive sources of aluminum and silicon, a templating agent and water.

BACKGROUND OF THE INVENTION

Naturally occurring clays such as dioctahedral smectites are composed ofsemicrystalline aluminosilicate layers (lamellae) held together by Vander Waals and electrostatic forces. Anionic charges on the siliceouslayers are neutralized by cations in the interlamellar spaces. Thesecations are usually sodium, calcium, or potassium. When these cationsare large oligomers of inorganic cations such as Fe⁺³, Cr⁺³ or when theyare metal hydroxy polymer cations such as [Al₁₃ O₄ (OH)₂₄ (H₂ O)₁₂ ]⁷⁺or [Zr(OH)₂.4H₂ O]₄ ⁸⁺, they act as pillars, propping the clay layersapart to afford a pillared layered clay. Upon heating, these oligomersor polymers are converted to the metal oxide, thus preventing thecollapse of the clay layers and thus pillaring the clay.

These smectite clays are known to catalyze reactions such as alkylation,cracking, ester formation, dimerization, oligomerization, etc. However,because the naturally occurring clays have a large variation in impuritycontent, industrial demand for the natural smectites has been verylimited. Therefore, attempts have been made to synthesize some of thesesmectite clays. For example, European Patent Application 163560discloses a method of preparing a beidellite clay (one of the smectiteclays). The process involves taking a mixture containing aluminumnitrate, tetraethylorthosilicate (TEOS), sodium carbonate and sodiumhydroxide, drying the mixture and then calcining to give aluminum oxide,silicon oxide, and sodium oxide, adding to that hydroxide anions andheating the resultant slurry to a temperature of about 340° C. for 14days. Although this method produces a beidellite that is purer than thenaturally occurring beidellite, the use of oxides leads to incompletereaction even though the synthesis is carried out at high temperatures.Additionally, the presence of sodium is detrimental to the catalysis ofcertain reactions and therefore, the sodium has to be replaced by someother cation.

Applicant has solved the problems with the synthesis of beidellite foundin the prior art by using a reaction mixture which contains a secondaryor tertiary amine, a quaternary ammonium salt or a quaternaryphosphonium salt along with reactive sources of aluminum and silicon.For example, tetramethylammonium hydroxide is mixed with alumina andcolloidal silica along with water at a pH of about 8.5 to about 14 andreacted at a temperature of 150°-210° C. for about 1 to 20 days toprovide a TMA⁺ -beidellite. The resultant product is also unique in thatunlike the beidellites which are described in the prior art, the instantproduct has crystals whose average crystallite size is about 50-150Angstroms, has a surface area of at least 80 m² /g, is substantiallyfree of sodium cations and has its 060 X-ray diffraction peak at ad-spacing of 1.50 Angstroms. The tetramethylammonium cations have takenthe place of sodium cations that are present in prior art beidelliteproducts. Although the prior art shows that a sodium beidellite can beexchanged with an alkyl ammonium compound the resultant exchange productdoes not have the same characteristics as the instant composition.

Although the prior art shows that quaternary ammonium compounds can beused to prepare some synthetic clays, there is no indication that anamine, a quaternary ammonium compound or a quaternary phosphoniumcompound could be used to prepare a synthetic beidellite. For example,R. M. Barrer and L. W. R. Dicks in J. Chem. Soc. (A), 1967, 1523-1529,have shown that alkyl ammonium compounds can be used to synthesizemontmorillonites and hectorites. Thus, applicant is the first tosynthesize an alkyl ammonium beidellite having small crystallites, alarge surface area and its 060 peak at a d-spacing of 1.50 Angstroms.

SUMMARY OF THE INVENTION

This invention relates to a clay composition, a method of preparing thecomposition, and a method of using the composition. Accordingly, oneembodiment of the invention is a beidellite layered clay compositionhaving the empirical formula

    A.sub.x [Al.sub.4 ](Si.sub.8-x Al.sub.x)(O.sub.20)(OH.sub.4)

where A is a templating agent and x is the moles of the templating agentand varies from about 0.1 to about 2.0, the composition characterized inthat it has crystals whose average crystallite size is about 50-150Angstroms, has a surface area of at least 80 m² /g, has its 060 X-raydiffraction peak at a d-spacing of 1.50 Angstroms and is substantiallyfree of sodium cations.

Another embodiment of the invention is a process for preparing abeidellite layered clay composition having the empirical formula

    A.sub.x [Al.sub.4 ](Si.sub.8-x Al.sub.x)(O.sub.20)(OH.sub.4)

where A is a templating agent and x is the moles of the templating agentand varies from about 0.1 to about 2.0, the composition characterized inthat it has crystals whose average crystallite size is about 50-150Angstroms, has a surface area of at least 80 m² /g, has its 060 X-raydiffraction peak at a d-spacing of 1.50 Angstroms and is substantiallyfree of sodium cations, the process comprising providing a reactionmixture at reaction conditions and for an effective time to produce thecomposition, the reaction mixture comprised of reactive sources ofaluminum and silicon, a templating agent and water, the reaction mixtureexpressed in terms of molar ratios by the formula

    aR:ySiO.sub.2 :zAl.sub.2 O.sub.3 :bH.sub.2 O

where R is at least one templating agent, a is the moles of R and ischosen such that the ratio of a:y varies from about 1 to about 20, y isthe moles of SiO₂ and varies from about 6.6 to about 7.8, z is the molesof Al₂ O₃ and varies from about 2.1 to about 2.7 and b is the moles ofwater and varies from about 40 to about 500.

Yet another embodiment of the invention is a hydrocarbon conversionprocess comprising contacting a hydrocarbon feed under hydrocarbonconversion conditions with a catalyst to give a hydroconverted product,the catalyst comprising a beidellite layered clay composition having theempirical formula

    A.sub.x [Al.sub.4 ](Si.sub.8-x Al.sub.x)(O.sub.20)(OH.sub.4)

where A is a templatiNg agent and x is the mole fraction of thetemplating agent and varies from about 0.1 to about 2.0, the compositioncharacterized in that it has crystals whose average crystallite size isabout 50-150 Angstroms, has a surface area of at least 80 m² /g, has its060 X-ray diffraction peak at a d-spacing of 1.50 Angstroms and issubstantially free of sodium cations.

Other objects and embodiments will become more apparent after a moredetailed description of the invention.

DETAILED DESCRIPTION OF THE INVENTION

As stated, this invention relates to a clay composition, a method ofpreparing the clay composition and a process using the composition. Thecomposition of the present invention is a beidellite clay. Beidellite isone of the smectite clays that has the empirical formula

    A.sub.x [Al.sub.4 ](Si.sub.8-x Al.sub.x)(O.sub.20)(OH.sub.4)

A is a templating agent and/or a counter ion and traditionally has beenan alkali metal. However, in the beidellite compositions of thisinvention A is not an alkali metal but is chosen from the groupconsisting of secondary and tertiary amines, quaternary ammonium ions,quaternary phosphonium ions and mixtures thereof. Specifically theamines and quaternary ions specified below which are used to prepare thebeidellite are present in the final clay composition of this invention.Finally, x is the moles of A and varies from about 0.1 to about 2.0.Other characteristics of the beidellite composition of this inventionwill be described hereinafter.

The composition of the instant invention is prepared from a reactionmixture which contains reactive sources of aluminum and silicon, atemplating agent and water. The reaction mixture is expressed in termsof molar ratios by the formula aR:ySiO₂ :zAl₂ O₃ :bH₂ O r19re R is atleast one templating agent, a is the moles of R and is chosen such thatthe ratio of a:y varies from about 1 to about 20, and preferably fromabout 5 to 10, y is the moles of SiO₂ and varies from about 6.6 to about7.8, z is the moles of Al₂ O₃ and varies from about 2.1 to about 2.7 andb is the moles of water and varies from about 40 to about 500.

The templating agents which can be used in preparing the claycomposition of this invention are secondary and tertiary amines,quaternary ammonium or quaternary phosphonium compounds, the latter twocompounds having the formula R'₄ M⁺ X⁻ where R' is an alkyl groupcontaining from 1 to 8 carbon atoms or an aryl group, M is nitrogen orphosphorus and X is carbonate, hydroxyl or halide. The quaternaryammonium compounds are preferred and especially preferred are thequaternary ammonium hydroxides. Illustrative of the quaternary compoundswhich can be used as templating agents are the hydroxide, carbonate,chloride, bromide, fluoride and iodide salts of the following cations:tetramethylammonium; tetraethylammonium; tetrapropylammonium;tetrabutylammonium; tetra-t-butylammonium; tetrapentylammonium;tetraphenylammonium; tetramethylphosphonium; tetraethylphosphonium;tetrapropylphosphonium and tetraphenylphosphonium. Illustrative of thesecondary and tertiary amines which can be used are di-n-propylamine,ethylbutylamine, tripropylamine, triethylamine, piperidine,2-methylpyridine, di-n-pentylamine, choline, andN,N-dimethylbenzylamine. It should be pointed out that mixtures oftemplating agents can also be used to prepare compositions of thisinvention. The amount of templating agent that is necessary isdetermined by the amount of silicon present in the mixture. It isnecessary that the ratio of the moles of templating agent to the molesof silicon in the mixture vary from about 1 to about 20 and preferablyfrom about 5 to about 10.

Another necessary component of the reaction mixture is a reactive sourceof aluminum. By reactive is meant a compound that is not fullycondensed. That is the compound still contains one or more hydroxidegroups or is hydrated. Illustrative examples of reactive sources ofaluminum include boehmite alumina, gibbsite alumina, aluminum hydroxide,aluminum alkoxides and mixtures thereof. If aluminum hydroxide is usedit is preferred to use freshly prepared aluminum hydroxide. Specificexamples of aluminum alkoxides include aluminum isopropoxide andaluminum t-butoxide. A further necessary component of the reactivemixture is a reactive sources of silicon. Illustrative of the reactivesources of silicon are colloidal silica, silicon alkoxide and mixturesthereof. Specific examples of silicon alkoxides includetetraethylorthosilicate and tetramethylorthosilicate. The ratio ofsilicon to aluminum in the reaction mixture can vary widely but forconvenience is chosen to be from about 0.01 to about 20 and preferablyfrom about 0.2 to about 10.

Having formed the reaction mixture, it is reacted at reaction conditionsfor an effective time to provide the desired composition. The reactionconditions necessary to produce the desired beidellite clay include abasic pH, i.e., greater than pH 7 and preferably from about 8.5 to about14. A basic pH is necessary to transport or mineralize the SiO₂ and tosolubilize the reactants. It should be pointed out that the higher thesilicon to aluminum ratio the the pH that is required to provide thedesired product at a reasonable rate. The pH of the mixture iscontrolled by adding ammonium hydroxide to the mixture or adding moretemplating agent. In addition to a basic pH, it is also necessary tocarry out the reaction at an elevated temperature from about 150° C. toabout 210° C. and preferably from about 175° C. to about 200° C. Finallythe reaction mixture is reacted under the above described reactionconditions at an effective time which ranges from about 1 to about 20days in order to produce the desired beidellite smectite clay.

As stated the beidellite clay that is obtained by the above describedprocedure is characterized in that it is composed of crystals whoseaverage crystallize size is about 50-150 Angstroms. The averagecrystallize size is determined from the X-ray diffraction pattern of thecomposition. The apparent crystallize length in the (hkl) direction,L_(hkl), can be calculated from the Scherrer equation ##EQU1## where λis the X-ray wavelength, β_(hkl) is the full width at half-maximum forthe peak corrected for instrumental broadening and Θ_(hkl) is thediffraction angle. It also has a surface area of at least 80 m² /g andis substantially free of sodium cations. By substantially free is meantthat less than 0.2 weight percent sodium is present in the composition.The source of these sodium atoms are impurities in the startingmaterials. Finally the instant clay composition has its 060 X-raydiffraction peak at a d-spacing of 1.50 Angstroms.

One way by which clays can be characterized is by their X-raydiffraction patterns. In general, di- and trioctahedral clays can becharacterized by the value of their b-parameter. The b-parameter, whichis related to the repeat unit length in the octahedral layer, can bedetermined from the position of the 060 reflection. For dioctahedralminerals this reflection has spacings between 1.48-1.50 Angstromswhereas for trioctahedral minerals it is between 1.53-1.55 Angstroms.See Crystal Structures of Minerals and their X-ray Diffraction, G. W.Brindley and G. Brown, Eds, Mineralogical Society, London, 1980.

The prior art discloses that beidellite has its 060 peak at a d-spacingof 1.49 Angstroms. However, the beidellite prepared according to thisinvention has its 060 peak at a d-spacing of 1.50 Angstroms. Thisindicates that the beidellite of the present invention is different fromthat described in the prior art.

The beidellite clay composition of this invention can be used as is orit can be pillared to catalyze various hydrocarbon processes. It ispreferred to catalyze the various hydrocarbon process with a pillaredbeidellite clay. The clay can be pillared using methods well known inthe art. Examples of pillars which are well known in the art arealumina, rare earth containing alumina, ZrO₂, TiO₂, Cr₂ O₃, SiO₂ andSi/Al (silica/alumina). As stated, these pillars are introduced bycombining the clay with an oligomer or polymer of the desired cation ormixture of cations at reaction conditions. For example, alumina pillarsmay be introduced by using aluminum chlorohydrate. Aluminumchlorohydrate (also known as aluminum chlorohydroxide) is a polymericmetal complex having the empirical formula

    Al.sub.2+n (OH).sub.2n Cl.sub.6

where n has a value of about 4 to 12. The preparation of this aluminumpolymer is generally known to those skilled in the art. See, forexample: Tsuitida and Kobayashi, J. Chem. Soc. Japan (Pure Chem. Sect.),64, 1268 (1943). Inoue, Osugi and Kanaji, J. Chem. Soc. Japan (Ind.Chem. Sec.), 61, 407 (1958).

A rare earth ACH is an ACH as described above which is modified toinclude one or more rare earth elements such as cerium, lanthanum,neodymium, europium, etc (all U.S. Pat. No. 4,952,544 which isincorporated by reference). The ACH polymer is modified with the rareearth by adding a soluble rare earth salt, preferably a water solublerare earth salt. Examples of rare earth salts are the nitrates, halides,sulfates and acetates. Preferred rare earth elements are cerium andlanthanum with cerium nitrate and lanthanum nitrate being the preferredsalts. The rare earth is introduced into the polymer or oligomerstructure by mixing the rare earth salt either in solution (waterpreferred) or as a solid with the ACH. The mixture is refluxed at atemperature of about 105° to about 145° C. for a time of about 24 toabout 100 hours. The molar ratio of rare earth (expressed as oxide,e.g., CeO₂) to alumina (Al₂ O₃) in the solution prior to refluxing isfrom about 1:52 to about 1:1.

Descriptions of oligomers or polymers of the other pillaring materialscan be found in the following references: 1) Si/Al--U.S. Pat. No.4,176,090; 2) zirconia-Clays and Clay Minerals, 27, 119 (1979) and U.S.Pat. No. 4,176,090; 3) titania--U.S. Pat. No. 4,176,090; 4) chromiumoxide--U.S. Pat. No. 4,216,188 and 5) silicon oxide--U.S. Pat. No.4,367,163, all of which are incorporated by reference.

These pillared clays are prepared by means well known in the art such asadding the beidellite clay to a solution containing a pillar precursor,i.e., oligomer or polymer, stirring, filtering, redispersing with water(one or more times), isolating, drying and calcining at about 300° toabout 800° for a time sufficient to fix the structure (preferably about3 hours).

As stated, beidellite clay compositions are used to catalyze hydrocarbonconversion processes such as alkylation, cracking, hydrocracking, esterformation, dimerization, oligomerization, etc. It is particularlypreferred to use the clay compositions of this invention whetherpillared or non-pillared to catalyze alkylation and hydrocrackingprocesses. The conditions necessary to carry out alkylation of aromaticcompounds are well known and are disclosed, for example, in U.S. Pat.Nos. 3,965,043 and 3,979,331 which are incorporated by reference.Generally the process can be carried out in a batch type or a continuoustype operation. In a batch type process, the catalyst, aromatic compoundand alkylating agent are placed in an autoclave and the pressureincreased, if necessary, in order to effect the reaction in the liquidphase. An excess amount of aromatic compound should be present,preferably in a range of about 2:1 to about 20:1 moles of aromaticcompound per mole of alkylating agent. The reaction is carried out at anelevated temperature since the rate of alkylation is undesirably low atroom temperature. Preferably the temperature is in the range of about40° to about 200° C. The process is carried out for a time of about 0.5to about 4 hours, after which the product is separated from the startingmaterials by conventional means.

If it is desired to carry out the process in a continuous manner, thecatalyst is placed in a reactor which is heated to the desired operatingtemperature and the pressure increased above atmospheric, if necessary.The aromatic compound and alkylating agent are flowed over the catalystbed at a predetermined liquid hourly space velocity sufficient to effectalkylation. The effluent is continuously withdrawn and conventionalseparation means used to isolate the desired product.

Hydrocracking conditions typically include a temperature in the range of400° to 1200° F. (204°-649° C.), preferably between 600° and 950° F.(316°-510° C.). Reaction pressures are in the range of atmospheric toabout 3,500 psig (24, 132 kPa g), preferably between 200 and 3000 psig(1379-20,685 kPa g). Contact times usually correspond to liquid hourlyspace velocities (LHSV) in the range of about 0.1 hr⁻¹ to 15 hr⁻¹,preferably between about 0.2 and 3 hr⁻¹. Hydrogen circulation rates arein the range of 1,000 to 50,000 standard cubic feet (scf) per barrel ofcharge (178-8,888 std. m³ /m³), preferably between 2,000 and 30,000 scfper barrel of charge (355-5,333 std. m³ /m³). Suitable hydrotreatingconditions are generally within the broad ranges of hydrocrackingconditions set out above.

The reaction zone effluent is normally removed from the catalyst bed,subjected to partial condensation and vapor-liquid separation and thenfractionated hydrogen, and if desired some or all of the unconvertedheavier materials, are recycled to the reactor. Alternatively, atwo-stage flow may be employed with the unconverted material beingpassed into a second reactor. Catalysts of the subject invention may beused in just one stage of such a process or may be used in both reactorstages.

Catalytic cracking processes are preferably carried out with the claycomposition using feedstocks such as gas oils, heavy naphthas,deasphalted crude oil residua, etc. with gasoline being the principaldesired product. Temperature conditions of 850° to 1100° F., LHSV valuesof 0.5 to 10 and pressure conditions of from about 0 to 50 psig aresuitable.

The following examples are presented in illustration of this inventionand are not intended as undue limitations on the generally broad scopeof the invention as set out in the appended claims.

EXAMPLE 1

In a container 30 g of tetramethylammonium hydroxide (TMAOH) weredissolved in 260 g of water. To this solution there were added 6.6 g ofALOOH. The slurry was mixed until homogeneous. While stirring rapidly,16.5 g of colloidal silica which has been ammonia stabilized (availablefrom DuPont Inc. and identified as Ludox™ AS-40) were added. The slurrywas stirred until homogeneous and then aged quiescently under autogenouspressure in a Parr Reactor (125 cc) for 2 days at 200° C. The productwas collected by centrifugation and washed with water until the residualTMAOH was removed. The product was then dried at 110° C. for 16 hours.XRD characterization of the product showed it to be beidellite. Thesurface area of the composition as determined by the B.E.T. method was100 m² /g.

EXAMPLE 2

The procedure set forth in Example 1 was followed using 33.2 g of Ludox™AS-40. The slurry was aged for 5 days at 200° C. XRD characterization ofthe product showed it to be beidellite. The surface area of thecomposition as determined by the B.E.T. method was 100 m² /g.

EXAMPLE 3

The procedure set forth in Example 1 was followed using 23 g of aluminumisopropoxide instead of the AIOOH. The slurry was aged for 2 days at200° C. XRD characterization of the product showed it to be beidellite.

EXAMPLE 4

The procedure set forth in Example 1 was followed using 30.1 g oftetraethylorthosilicate (TEOS). The slurry was aged for 2 days at 200°C. XRD characterization of the product showed it to be beidellite. Thesurface area of the composition as determined by the B.E.T. method was120 m² /g.

EXAMPLE 5

The procedure set forth in Example 1 was followed using 10 g of TMAOHand 12 g of TMACI instead of the 30 g of TMAOH. The slurry was aged for10 days at 200° C. XRD characterization of the product showed it to bebeidellite.

EXAMPLE 6

The procedure set forth in Example 1 was followed using 30 g of TMAHCO₃.The slurry was aged for 10 days at 200° C. XRD characterization of theproduct showed it to be beidellite.

EXAMPLE 7

A solution of 12 g of ACH solution (Reheis™) in 500 g of water wasprepared. To this solution there were added 10 g of the TMA-beidelliteclay prepared in Example 1. The slurry was heated to 60° C. and agedwith stirring for 2 hours. After cooling to room temperature, the claywas recovered by centrifugation and washed with water untilsubstantially chloride free. The product was dried at 60° C. for 16hours. The sample was characterized by its X-ray diffraction patternwhich showed a d.sub.(001) spacing of 18.9 Angstroms and by N₂adsorption which showed a BET surface area of 265 m² /g.

The cracking activity of this pillared clay was determined using thefollowing heptene cracking test. The heptene cracking test uses anelectrically heated reactor which is loaded with 125 mg of 40-60 mesh(420-250 microns) particles of the catalyst to be tested. The catalystwas dried in situ for 30 minutes at 200° C. using flowing hydrogen, andthen subjected to a reduction treatment of 425° C. in flowing hydrogenfor one hour. The temperature of the reactor was then adjusted to 425°C. (inlet). The feed stream used to test the catalyst consists ofhydrogen gas which is saturated with 1-heptene at 0° C. and atmosphericpressure. The feed stream was flowed over the catalyst at a flow rate of125 cc/min. The effluent gas stream was analyzed using a gaschromatograph in order to calculate weight percent cracked product.Cracked product is product that has a lower molecular weight than thestarting 1-heptene hydrocarbon.

The ACH pillared beidellite had a cracking activity of 65 weightpercent.

The clay from Example 2 was pillared according to the procedure ofExample 7 and was tested using the heptene cracking test and showed acracking activity of 52 weight percent.

I claim as my invention:
 1. A beidellite layered clay composition having the empirical formula

    A.sub.x [Al.sub.4 ](Si.sub.8-x Al.sub.x)(O.sub.20)(OH.sub.4)

where A is a templating agent and x is the moles of the templating agent and varies from about 0.1 to about 2.0, the compostion characterized in that it has crystals whose average crystallite size is about 50-150 Angstroms, has a surface area of at least 80 m² /g, has its 060 X-ray diffraction peak at a d-spacing of 1.50 Angstroms and is substantially free of sodium cations.
 2. The composition of claim 1 where the clay layers are separated by pillars selected from the group consisting of alumina, rare earth containing alumina, ZrO₂, TiO₂, Cr₂ O₃, SiO₂ and silica/alumina.
 3. The composition of claim 2 where the pillar is alumina.
 4. The composition of claim 2 where the pillar is a rare earth containing alumina.
 5. The composition of claim 1 where A is selected from the group consisting of secondary amines, tertiary amines, quaternary ammonium ions, quaternary phosphonium ions and mixtures thereof.
 6. The composition of claim 5 where the quaternary ammonium ions are selected from the group consisting of tetramethylammonium ion, tetraethylammonium ion tetrapropylammonium ion, tetrabutylammonium ion, tetra-t-butylammonium ion, tetrapentylammonium ion, tetraphenylammonium ion and mixtures thereof.
 7. A process for preparing a beidellite layered clay composition having the empirical formula

    A.sub.x [Al.sub.4 ](Si.sub.8-x Al.sub.x)(O.sub.20)(OH.sub.4)

where A is a templating agent and x is the moles of the templating agent and varies from about 0.1 to about 2.0, the composition characterized in that it has crystals whose average crystallite size is about 50-150 Angstroms, has a surface area of at least 80 m² /g, has its 060 X-ray diffraction peak at a d-spacing of 1.50 Angstroms and is substantially free of sodium cations, the process comprising providing a reaction mixture at reaction conditions and for an effective time to produce the composition, the reaction mixture comprised of reactive sources of aluminum and silicon, a templating agent and water, the reaction mixture expressed in terms of molar ratios by the formula

    aR:ySiO.sub.2 :zAl.sub.2 O.sub.3 :bH.sub.2 O

where R is at least one templating agent, a is the moles of R and is chosen such that the ratio of a:y varies from about 1 to about 20, y is the moles of SiO₂ and varies from about 6.6 to about 7.8, z is the moles of Al₂ O₃ and varies from about 2.1 to about 2.7 and b is the moles of water and varies from about 40 to about
 500. 8. The process of claim 7 where the reaction conditions are a pH of about 8.5 to about 14 and a temperature of about 150° to about 210° C.
 9. The process of claim 7 where the mixture is reacted for a time of about 1 to about 20 days.
 10. The process of claim 7 where the templating agent, R, is selected from the group consisting of secondary amines, tertiary amines, quaternary ammonium compounds, quaternary phosphonium compounds and mixtures thereof, the quaternary compounds having the formula R'₄ M⁺ X⁻, where R' is an alkyl group containing from 1 to 8 carbon atoms or an aryl group, M is nitrogen or phosphorus and X is hydroxyl, carbonate or halide.
 11. The process of claim 7 where the templating agent, R, is a quaternary ammonium compound selected from the group consisting of tetramethylammonium salts, tetraethylammonium salts, tetrapropylammonium salts, tetrabutylammonium salts, tetra-t-butylammonium salts, tetrapentylammonium salts, tetraphenylammonium salts and mixtures thereof. 